Optimised hydrogen production by
steam reforming: part I
Modelling optimisation of process and design parameters for minimising
natural gas consumption in hydrogen production by steam reforming
Sanke Rajyalakshmi, Kedar Patwardhan and P V Balaramakrishna
Larsen and Toubro
H
ydrogen is a particularly
important feedstock in
refineries because of
stringent environmental legisla-
tion for producing low-sulphur
gasoline and diesel fuels. The
refinery hydrogen requirement
is fulfilled through the route of
steam methane reforming
(SMR) of natural gas. SMR is a
highly energy-intensive tech-
nology and this energy
requirement can be minimised
by combining various reform-
ing techniques. In this article,
process optimisation of the
hydrogen plant is carried out
to minimise natural gas
consumption by considering
operating parameters such as
the steam-to-carbon ratio, vari-
ous reactor configurations,
methane slip, choice of product
purification step, and natural
gas composition in a conven-
tional SMR process.
In a second article to follow,
new process schemes incorpo-
rating an autothermal reformer
(ATR) and a heat exchange
reformer (in series and parallel
combination with the ATR)
offered by licensors are evalu-
ated and compared with the
conventional process. It has
www.digitalrefining.com/article/1000339
been observed that the new
schemes, from the point of view
of natural gas consumption, are
more beneficial compared with
the conventional process but at
a cost of lower steam produc-
tion from the hydrogen plant.
Hence, where the natural gas
price is substantial and domi-
nates the plant operating cost,
the new process scheme should
be utilised.
Along with increased hydro-
gen consumption for deeper
hydrotreating, additional
hydrogen is needed for process-
ing heavier and higher sulphur
crude slates. In many refineries,
hydroprocessing capacity and
the associated hydrogen
network limits refinery
throughput and operating
margins. Furthermore, higher
hydrogen purities within the
refinery network are becoming
more important to boost
hydrotreater capacity, achieve
product value improvements
and lengthen catalyst life
cycles. Improved hydrogen
utilisation and expanded or
new sources for refinery hydro-
gen and hydrogen purity
optimisation are now required
to meet the needs of the future
market for transportation fuels
and the drive towards higher
refinery profitability.
A variety of process technolo-
gies can be used for hydrogen
production, including steam
reforming, cracking, gasifica-
tion and electrolysis. The choice
depends on the scale of produc-
tion required and the cost of
available feedstocks.
For large-scale production,
the steam reforming of natural
gas has become the preferred
solution. In some cases, partial
oxidation has also been used,
particularly where heavy oil is
available at low cost. However,
oxygen is then required and
the capital cost of producing
oxygen plant makes partial
oxidation expensive. On the
other hand, the steam reform-
ing of natural gas offers an
efficient, economical and
widely used process for hydro-
gen production, and provides
near- and mid-term energy
security and environmental
benefits. The efficiency of the
steam reforming process is
about 65% to 75%, among the
highest of current commer-
cially available production
methods.
PTQ Q1 2012 1
 BFW water
(from BL)
NG
(from BL)
Feed
pretreatment
Natural gas (secondary fuel)
Steam
export
Waste heat
recovery
Figure 1 Typical steam methane reformed hydrogen plant block diagram
The SMR process is divided
into sections: feedstock purifi-
cation for the removal of
sulphur and other impurities;
steam reforming for synthesis
gas generation; shift conver-
sion/carbon monoxide removal;
and hydrogen purification. A
general block diagram with
natural gas as the feedstock is
shown in Figure 1.
Natural gas feed is preheated
in coils in the waste heat
section of the reformer, and
sulphur is removed over a zinc
oxide catalyst. Process steam is
added, and the mixture of
natural gas and steam is further
preheated before entering the
tubular reformer. Here, conver-
sion to equilibrium of
hydrocarbons to hydrogen,
carbon monoxide and carbon
dioxide takes place over a
nickel-based reforming catalyst.
The gas exits the reformer and
is cooled by steam production
before entering the shift
converter. Over the shift cata-
lyst more hydrogen is produced
by converting carbon monoxide
and steam to carbon dioxide
and hydrogen. The shifted gas
2 PTQ Q1 2012
PSA off gases (primary fuel)
Steam CO-shift
reformer converter
Heat
recovery-I recovery-II
is cooled further to an ambient
temperature before entering the
pressure swing adsorption
(PSA) unit. High-purity hydro-
gen product is obtained, and
the off-gas from the PSA unit is
used in the reformer as fuel
supplemented with natural gas
fuel. Combustion air for the
tubular reformer burners can
be preheated in coils in the
reformer waste heat section.
Part of the steam produced in
the hydrogen plant is used as
process steam; the excess steam
is exported.
The objective of this study is
to analyse the process parame-
ters of the present configuration
and to identify optimum condi-
tions to enhance the process
performance. Different process
layouts with high, medium-
and low-temperature shift
reactors and also with different
purification processes (PSA and
methanator) are studied and
compared.
Identification and optimisation
of process parameters
The study focuses on the opti-
misation of process/design
H2 H2
purification (to BL)
Heat
Process
condensate
stripper
parameters for the minimisation
of natural gas consumption. The
study is particularly useful in
countries such as India, where
natural gas prices dominate
operating cost. The most impor-
tant parameters to influence
natural gas consumption are:
• Methane slip
• Steam-to-carbon ratio
• Natural gas composition
• Shift converter configuration
• Choice of hydrogen purifica-
tion step.
The following assumptions
were made while carrying out
the analysis:
• Impurities in feed are effi-
ciently removed in the feed
purification stage. The total
volume of reactors in the puri-
fication stage does not change
within the variation of operat-
ing parameters under study
• Hydrogen production is fixed
at 90 000 Nm3/h for any varia-
tion in the operating parameter
• PSA efficiency is 89%
• The kinetics of the reaction
are taken from the open litera-
ture and are not specifically
applicable to any particular
catalyst.
www.digitalrefining.com/article/1000339
Methane slip
The steam methane reforming 50000
reaction is strongly endother-

Natural gas consumption,

mic and is therefore favoured 40000
by a higher temperature.
Typical reformer outlet temper-
30000
atures fall in the range

Nm3/hr
810–900°C. As the temperature
is increased, the hydrogen yield 20000
increases, which is observed as
a reduction in the methane 10000 NG feed
concentration in the reformer NG fuel
effluent, known as methane Total NG
0
slip. The higher the yield, the 0 1 2 3 4 5 6 7
less the amount of feedstock Methane slip, %
that will be consumed.
Due to the lower methane Figure 2 Effect of methane slip on natural gas consumption
slip, the calorific value of the
PSA off-gas is reduced and, carbon contained in the hydro- increase in feedstock consump-
since this stream is the base carbon gas. A higher tion, which is almost balanced
load fuel for the reformer, the steam-to-carbon ratio drives the by a decrease in demand for
supplementary fuel (natural reaction closer to the equilib- supplementary fuel (see Figure
gas) imported to the hydrogen rium and increases the 3). The mechanism of these
unit increases (see Figure 2). hydrogen yield. effects is opposite to that for a
This effect is enhanced because Reforming catalysts require higher reformer outlet tempera-
the higher reformer outlet steam to be present in excess, ture, in that the methane slip
temperature increases its radi- increasing the volumetric increases and the PSA off-gas
ant duty. The supplementary throughput and cost of the contains more calorific value.
fuel has a relatively small flow plant, so there is always interest The decrease in steam-to-carbon
and is strongly influenced by in reducing the steam-to-carbon ratio gives rise to an increase in
small changes to the reformer ratio. In doing so, there is an the reformer radiant duty,
heat balance so that, in this
case, there is a small increase in
the total feed/fuel consump- 60000
tion. This effect is due to the
increase in radiant duty and 50000
reduction in the steam require-
Natural gas, Nm3/hr

ment for the process feed,

40000
giving the net increase in the
steam available for export. The
higher reformer outlet tempera- 30000
ture shifts the heat balance to
produce more steam from more 20000
feed/fuel.

10000 NG feed
Steam-to-carbon ratio NG fuel
The feed gas to the reformer is Total NG
a mixture of steam and hydro- 0
carbon gas. The mixture is 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
characterised by the steam-to- S/C ratio
carbon ratio, which is the molar
ratio of steam to the reactive Figure 3 A wide range of ADZs for all applications

www.digitalrefining.com/article/1000339 PTQ Q1 2012 3


46000
44000
Total NG consumption,
42000
40000
Nm3/hr
38000
36000
34000
32000
30000
8000
Figure 4 Effect of methane content in natural gas on specific energy
which increases the steam
generated in the convection
section. Less steam is used in
the process and the steam
exported from the plant is
further increased. In this case,
the significant benefit of a lower
steam-to-carbon ratio is clearly
shown. A lower steam-to-carbon
ratio is limited by the catalyst
performance and tendency of
the feedstock to form carbon at
the reformer inlet.
Natural gas composition
Natural gas mainly contains
methane in the range (75–98%
by volume) along with higher
hydrocarbons (C2+ compo-
nents) and inert gases. The
higher hydrocarbons contribute
to the calorific value of the
natural gas as well the hydro-
gen production. The inerts in
natural gas add only to the
natural gas volumetric flow
rate and thus contribute only to
capital cost (due to an increase
in the piping and equipment
sizes) and operating cost
(higher power consumption in
compressor). The cost of the
natural gas is calculated on the
basis of the calorific value.
Here it should be noticed that
higher HC content in the
4 PTQ Q1 2012 www.digitalrefining.com/article/1000339
From Figure 4, it can be seen
11150
that even though NG consump-
tion reduces with the increase
11100
Operating cost, $/hr
in calorific value, the operating
11050 cost increases.
11000
Shift reactor configuration
10950
A typical steam-to-carbon ratio
in a configuration containing an
NG consumption 10900 HTS reactor is 2.8. The steam-
Operating costs to-carbon ratio will depend not
10850
8500 9000 9500 10000 10500 11000 11500
only on the pre-reformer/
NG calorific value, Kcal/Nm3 reformer catalyst but also on the
type of shift converter catalyst.
All HTS catalysts are based on
Fe-Cr oxides that over-reduce
natural gas contributes to when the steam-to-hydrogen
higher hydrogen production ratio drops below certain limits.
for the same quantity of feed The consequence of this over-
gas. Hence, the natural gas reduction is the formation of
consumption as feed decreases higher hydrocarbons and
with the calorific value. Higher oxygenates by the Fischer-
HC in the feed also contributes Tropsch reaction.
to more CO2, resulting in The steam-to-dry gas ratio
higher off-gases from the PSA. will be 0.46–0.52 for HTS cata-
Thus, for the same methane lysts and 0.39 for MTS catalyst
slip, the contribution from the at the converter inlet. Different
off-gas is more in the case of shift converter configurations
higher HC natural gas, result- were studied by fixing the
ing in a reduction in the natural gas feed flow rate and
supplementary NG fuel the steam-to-carbon ratio. The
requirement. The following reformer outlet temperature is
graph is plotted as calorific maintained at 860°C. A
value against the total NG prereformer/reformer/HTS/
consumption for the given LTS scheme is optimum and
hydrogen production. The provides ~3.5% savings in
graph also provides the operat- natural gas consumption over a
ing cost for the natural gas for reformer/HTS combination
the hydrogen plant within the (see Figure 5a).
range of calorific values consid- The prereformer helps in the
ered. The operating cost is reduction of natural gas
calculated by multiplying x- consumption as feed as well as
axis and y-axis value by the fuel. Above that, the prere-
NG unit cost, which is consid- former offers other advantages
ered as 29$/Gcal with reference such as flexibility in handling
to the Indian scenario. Hence, natural gas feed composition, a
for case 1, the operating cost reduction in reformer heat
due to NG works out to be: duty, and reformer catalyst
protection. Hence, it has
=8565(X-axis value, Kcal/Nm3)*43878(Y- become an essential part of
axis value, Nm3/hr) *29($/Gcal) hydrogen plants. Even though
= 10899$/hr. MTS saves on natural gas
consumption, the catalyst
volume requirement is very 
 8JUI
QSFSFGPSNFS
high compared to other shift

Re l at i ve t o
t al NG
con su mpt i on ,

8JUIPVU
QSFSFGPSNFS
configurations (see Figure 5a).

As a result, MTS is only used 
 
for smaller capacity hydrogen

plants, while for larger plants it
is used in combination with

%


LTS. 


Hydrogen purification
In modern plants, PSA is used 
for the final hydrogen purifica-
tion instead of CO2 absorption 
followed by a methanator. PSA HTS HTS+LTS MTS
gives a high-purity hydrogen
product of 98–99%, while an Figure 5a Effect of shift reactor configuration on natural gas consumption
absorption/methanator combi-
nation provides purities in the
range 90–94% (see Figure 5b). 5
Natural gas consumption will With prereformer
Relative catalyst volume

be 12% less than with a PSA 4

purification step. Hence, in
refinery operations where
hydrogen purity is not essen-
tial, a hydrogen plant with the
later combination may be
preferred.
Generation of base case with
optimised parameters and
comparison with operating data
Overall hydrogen production
depends upon the consumption
of utilities, which typically
include feed, fuel, boiler feed
water, electrical power, cooling
water and steam production/
import. Of these utilities, feed
and fuel contribute more than
90% of the total utilities cost.
The major utility besides natu-
ral gas is steam, as it is
produced as by-product in the
plant. The credit given for
export steam can have a signifi-
cant impact on utility costs,
especially when refinery utility
costs are favourable for steam
production.
The steam produced in the
plant has internal consumers
Without prereformer
3
2
1
0
0 HTS HTS LTS MTS
(HTS+LTS) (HTS+LTS)
Figure 5b Catalyst requirement for shift reactor configuration
within boundary limits. Most Conclusion
important among them are Natural gas offers greater advan-
steam-driven turbines for BFW tages over other feedstocks for
pumps, ID and FD fans, proc- hydrogen production in terms of
ess steam for reforming, simplicity of use, operating cost
process condensate stripper, and capital cost. For economic
while other consumers include production of hydrogen utilities
steam tracing, lube oil heating, such as natural gas as feed, fuel
losses and so on. Steam produc- and steam are the important
tion within the plant should be parameters. However, steam
adequate for these contributors, export is important only when
and surplus steam is exported. there is a need from other parts
A simulation carried out for the of the refinery. Hence, the over-
entire hydrogen plant is shown all objective should be to
in Table 1, along with the set of minimise natural gas consump-
optimised parameters studied. tion for the hydrogen plant.

www.digitalrefining.com/article/1000339 PTQ Q1 2012 5

 Kedar Patwardhan is a Senior Process
Utilities consumption in a hydrogen plant Engineer with the Chemical Engineering
Group of Larsen and Toubro, specialising
Operating parameters Calculated Reference I Reference II Reference III in simulation, modelling and process
Approx. capacity, Nm3/hr 50 000 100 000 40 000
Methane slip 3.92 6.74 2.69 6.74
design. He holds a PhD from the Institute
Steam-to-carbon ratio 2.6 2 2.59 2.0 of Chemical Technology, Mumbai. Email:
NCV, Kcal/Nm3 11 211 9393 9765 9393 kedar_patwardhan@lntenc.com
Shift reactor configuration MTS+LTS MTS MTS+LTS MTS P V Balaramakrishna is Head of the
Purification step PSA PSA PSA PSA
Utilities, per Nm of hydrogen
3
Calculated Reference I Reference II Reference III Chemical Engineering Group of Larsen
Natural gas feed, Nm3/Nm3 0.257 0.352 0.278 0.352 and Toubro, specialising in process design,
Natural gas fuel, Nm3/Nm3 0.064 0.025 0.086 0.023 advanced process control and process
Total feed + fuel, Nm3/Nm3 0.321 0.377 0.363 0.375
HP export steam, kg/Nm3 0.424 0.695 0.620 0.674 plant optimisation. He holds a master’s
Electric power, kWH/Nm3 0.0012 0.017 0.038 0.017 in chem engineering from the Indian
BFW requirement, kg/Nm3 1.222 1.166 1.142 1.145 Institute of Technology, Kanpur.
CW req., kg/Nm 3
2.34 1.9 11.3 1.9
Email: pv_balaramakrishna@lntenc.com

Table 1

Hydrogen plant capacity, end Sanke Rajyalakshmi is a Process Engineer

use and export steam require-
ment usually govern the
selection of an optimum set of
operating parameters for a new
hydrogen plant.
Links
specialising in simulation with the
Chemical Engineering Group of Larsen and
Toubro, Powai, India. She holds a master’s More articles from the following
category:
in chemical engineering from the National
Institute of Technology, Warangal. Reforming
Email: rajya_sanke@lntenc.com

6 PTQ Q1 2012 www.digitalrefining.com/article/1000339